7,7a-epoxy-5,6,7a-tetrahydro-1,1,2,3,3-pentamethyl 4(3ah)-indanone perfume composition

ABSTRACT

Indanone derivatives having the formula   Wherein one of R.sub.1 and R.sub.2 is O and the other is H.sub.2 ; Y is H or, taken together with X, an epoxy oxygen; one of the single dashed lines represents a double bond, which is present unless said epoxy oxygen is present, and when R.sub.2 is O and the double bond is conjugated with R.sub.2, X is H; perfume compositions containing such indanones and processes for producing same.

United States Patent [191 Hall [ 7,7A-EPOXY-5,6,7A-TETRAHYDRO- l,l,2,3,3-PENTAMETHYL 4(3AH)-INDANONE PERFUME COMPOSITION [75] Inventor: John B. Hall, Rumson. NJ.

[73] Assignee: International Flavors & Fragrances lnc., New York, NY.

22 Filed: Mar. 4, 1974 [21] Appl. No.: 447,662

Related US. Application Data [62] Division of Ser. No. 325.677. Jan. 22, I973. Pat. NO.

3,816,350. which is a division of Ser. No. 851,049.

Aug. 18. W69. Pat. No. 3773.836.

[52] US. Cl. 252/522 [51] lnt.Cl Cllb 9/00 [58] Field of Search 260/348 C; 252/522 [56] References Cited UNITED STATES PATENTS 3,839,368 l0/l974 Hall 260/348 C Apr. s, 1975 Primary E.\'aminerVeronica OKeefe Attorney. Agent. or Firm-Brooks Haidt & Haffner [57] ABSTRACT lndanone derivatives having the formula 1 Claim, N0 Drawings BACKGROUND OF THE INVENTION There is a continuing need for fragrance materials having persistent musk \voody odors with satisfactory overtones or qualities. While many natural products have musk and/or \voody fragrances. the more desirable of these are not only frequently in short supply and hence difficult to obtain and expensive. but the combination of the olfactory qualities is rare. Moreover. it is also most desirable that such musk woody fragrance character have good persistence so that the substances can be used in quality formulations for perfume or other olfactory compositions. Such materials should also possess good blending qualities so that they are useful in preparing perfume compositions.

THE INVENTION Briefly, the present invention provides novel indanones having the structural formula'.

wherein one ofR, and R is O and the other is H It will be observed that these compositions also include the 7,7a-epoxy derivative. and the foregoing formula encompasses such monounsaturated and saturated epoxy indanones. Accordingly. Y is H or, taken together with X, an epoxy oxygen, and one of the single dashed lines represents the double bond unless said epoxy oxygen is present. When the double bond is conjugated with R (when this latter is then X is H.

These substances have strong, persistent, musk woody odors with various rich amber, precious woody, or fine woody overtones. Thus, the present invention also provides novel perfume and fragrance compositions containing such indanones, and processes for producing such indanones are also disclosed herein.

More specifically, the indanone derivatives contemplated herein are 6, 7-dihydro-l,l,2,3,3-pentamethyl- 4(5H)-indanone having the formula:

2 6.7-dihydro-l.1,2.3,3-pentamethyl-5(4H)-indanone having the formula 7.7a-dihydro-1,l,2,3,3-pentamethy1-5(6H)-indanone having the formula and 7.7a-epoxy-5.6,6.6u-tetrahydro-1.1,2,3.3-pentamethyl- 4(3aH)-indanone having the formula:

It will be appreciated by those skilled in the art from the present disclosure that the materials according to this invention can exist in several stereoisomeric forms. It is contemplated that the formulas given herein include the several isomeric forms.

A convenient starting material according to the present invention is pentamethylindane. The pentamethylindane is hydrogenated to provide the tetrahydro derivative as the first step in the synthesis of the 4- indanones. The six-membered ring is then oxidized with a suitable agent to obtain a mixture of the monounsaturated indanone and the epoxy indanone. The hydrogenation is carried out under controlled conditions to add 2 moles of hydrogen to each mole of the indane. It is preferred to use metallic catalysts such as Raney nickel or noble metals such as palladium, rhodium, and the like.

The hydrogenation is carried out at substantially superatmospheric pressures of from 50 to 200 atmospheres, and is preferably carried out at from 60 to about atmospheres. The reaction is desirably carried out at temperatures in excess of 100C up to 225C, and a preferred temperature range is to C.

The 4,5,6,7-tetrahydropentamethylindane so obtained is then oxidized to provide the substituent or substituents on the six-membered ring. The oxidation is carried out with an oxidizer such as a hexavalent chromium compound. selenium dioxide. and the like. In preferred embodiments of the process. chromium trioxide or alkali metal dichromate such as sodium dichromate. potassium dichromate. and the like are used.

This reaction can be carried out at pressures above or below atmospheric. but atmospheric pressure is desired to minimize ebullition of any reaction vehicle and provide an acceptable reaction rate. while maintaining control over the reaction. The temperatures used are in the range of to 70C. and are preferably in the range of from 40 to 60C.

The reaction is preferably carried out in the presence of a vehicle. and acidic vehicles are desirable. Such reaction vehicles include lower alkanoic acids having up to three or four carbon atoms. and acetic acid is a preferred vehicle.

The S-indanone can be prepared by producing the 5-indanol (a phenol) and hydrogenating it to obtain the 4.5.6.7-tetrahydro derivative or by reducing the phenol or its lower alkyl ether by means of a Birch reduction. The S-indanol is produced by treatment of 1.1 .2.3.3pentamethylindane with an acyl halide such as acetyl chloride in the presence of a Friedel-Crafts catalyst to provide the indanyl-lower alkyl ketone. The ketone is then oxidized to the corresponding ester with a percarboxylic acid such as peracetic acid. and the indanol is obtained therefrom by hydrolysis with a strong alkali such as potassium hydroxide.

The indanol is treated with sodium hydride or another alkali metal hydride in a reaction vehicle. preferably a solvent such as dimethyl formamide to form the alkali metal alcoholate. This reaction can be carried out at temperatures of C to 70C, preferably from 40 to 55C. The ester is then produced by treatment of the alcoholate with a lower dialkyl sulfate such as dimethyl-sulfate.

The S-indanyl ester is reduced according to the Birch technique to obtain a ketone mixture. The Birch reduction is carried out with an alkali metal, preferably lithium. in liquid or gaseous ammonia. This reaction is carried out at from 40C to C. The pressure at which this reaction is carried out ranges from atmospheric or slightly subatmospheric up to about five atmospheres. Thus. at 33C the reaction can be carried out at one atmosphere in liquid ammonia. while at 20-25C the reaction is carried out at five atmospheres.

The ketones produced according to the above reaction schemes can be separated from the vehicle and any unreacted materials or unwanted by-products removed by conventional means including washing, distillation. crystallization. extraction. preparative chromatography, and the like. It is preferred to fractionally distill the washed reaction product under a relatively high vacuum so as to obtain a relatively pure mixture of unsaturated ketones. Product purities of 80% are readily obtained, and much higher purities can also be provided by suitable treatment. The individual ketones can also be obtained by similar techniques. All parts. proportions, percentages and ratios herein are by weight unless otherwise indicated.

The pentamethylindanones and epoxides of this invention are useful as fragrances. They can be used sin-- gly or in combination to contribute a woody musk fragrance. As olfactory agents the indanones of this invention may be formulated into or used as components of a perfume composition.

The term perfume composition" is used herein to mean a mixture of organic compounds. including, for example, alcohols, aldehydes. ketones. esters and frequently hydrocarbons which are admixed so that the combined odors of the individual components produce a pleasant or desired fragrance. Such perfume compositions usually contain: (a) the main note or the bouquet or foundation-stone of the composition; (b) modifiers which round-off and accompany the main note; (0) fixatives which include odorous substances which lend a particular note to the perfume throughout all stages of evaporation, and substances which retard evaporation; and (d) top-notes which are usually lowboiling fresh-smelling materials.

In perfume compositions the individual component will contribute its particular olfactory characteristics. but the overall effect of the perfume composition will be the sum of the effect of each ingredient. Thus. the individual compounds of this invention, or mixtures thereof. can be used to alter the aroma characteristics of a perfume composition, for example. by highlighting or moderating the olfactory reaction contributed by another ingredient in the composition.

The amount of the compounds of this invention which will be effective in perfume compositions depends on many factors. including the other ingredients,-

their amounts and the effects which are desired. It has been found that perfume compositions containing at little as 2% by weightof mixtures or compounds of this invention. or even less. may be used to impart a woody musk odor to soaps. cosmetics, and other products. The amount employed can range up to 7% or higher and will depend on considerations of cost. nature of the end product. the effect desired on the finished product. and the particular fragrance sought.

The partially saturated and epoxy indanones of this invention can be used alone or in a perfume composition as olfactory components in detergents and soaps; space deodorants; perfumes; colognes; bath preparations such as bath oil. bath salts; hair preparations such as lacquers. brilliantines, pomades, and shampoos; cosmetic preparations such as creams, deodorants. hand lotions, sun screens; powders such as talcs. dusting powders. face powder, and the like. When used asan olfactory component of a perfumed article, as little as 0.01 1% of one or more of the novel ketones will suffice to impart a fine woody musk odor.

in addition. the perfume composition can contain a vehicle or carrier for the other ingredients. The vehicle can be a liquid such as alcohol, glycol, or the like. The carrier can be an absorbent solid such as a gum or components for encapsulating the composition.

It will also be appreciated that the pentamethylindanone derivatives according to this invention can be used to enhance, alter, modify, or supplement the fragrance properties of natural or synthetic fragrance compositions. Thus, such indanones can be used in fragrance compositions for addition to perfume compositions or directly to products such as soap, detergents, cosmetics, and the like. The fragrance compositions so prepared do not entirely provide the olfactory properties to the finished perfume or other article, but they do furnish a substantial part of the overall fragrance impression.

The following examples are given to illustrate embodiments of the invention as it is presently preferred to practice it. It will be understood that these examples are illustrative, and the invention is not to be considered as restricted thereto except as indicated in the appended claims.

EXAMPLE 1 Enough hydrogen is fed into the autoclave to raise the pressure to 1.000 psig. The hydrogen feed is then continued and the autoclave is heated to a temperature in the range of l50185C over a period of about 8 hours until an amount of hydrogen equal to 10% in excess of theory is absorbed. During this time the pressure in the autoclave is maintained at 1.500 psig.

The 1.641 grams of crude product removed from the autoclave is distilled on a 12-inch Goodloe column after being mixed with 10.0 grams of Primol mineral oil. The distillate is recovered in two fractions:

Fraction 1'. Distills at a temperature of 80C and 4.0

mm Hg to provide 401 grams of 4.5.6.7-tetrahydro- 1 .1.2,3,3-pentamethylindane.

Fraction II: Distills at a temperature of 86-88C and 3.5-3.8 mm Hg to provide 729 grams of hexahydro- 1. l .2.3.B-pentamethylindane.

A sample of Fraction 1 is further refined on a 6-foot by three-quarter-inch gas liquid chromatographic (GLC) column containing Carbowax polyethylene glycol and operated at 1 10C. Analysis by infrared (IR) and proton magnetic resonance (PMR) confirms the structure:

b. Production of 6.7-Dihydro-l.l,2,3,3-pentamethyl- 4(5H)-indanone and 7,7a-Epoxy-5.6,7.7a-tetrahydro- 1,1.2,3,3-pentamethyl-4(3aH)-indanone Into a 2-liter round-bottom flask equipped with thermometer, stirrer, heating mantle and the reflux condenser is placed 194 g of the tetrahydropentamethylindane produced by the foregoing procedure. The contents of the flask are heated to 50C and a solution of 298 grams of sodium bichromate (Na- Cr O-jH O) in 1.200 ml of acetic acid is added during two hours while 5 the temperature is maintained at 50C. After addition is complete. the reaction mass is heated at 100C and maintained at that temperature for five hours.

The reaction mass is then cooled to C, and 500 m1 of toluene and 2 liters of water are added. The mixture 10 is stirred for 15 minutes and the aqueous phase is then separated from the organic phase. The aqueous phase is extracted with one 500 ml volume of toluene and the toluene extract is then combined with the original organic phase. The combined organic material is washed successively with an equal volume of water. an equal volume of saturated aqueous sodium bicarbonate. and an equal volume of water.

The solvent is stripped off the washed material to yield a crude product weighing 198 grams. This crude product is distilled at a vapor temperature of from 93C 106C and 3.0 mm Hg yielding a product weighing 86.0 grams. This vacuum-distilled product is redistilled on a 12-inch Seavy column at a vapor temperature of 75C 89C and 2.4 mm Hg. A sample ofthe redistilled material is separated into pure components on an eightfoot by /s-inch GLC column at 160C using 10% Carbowax polyethylene glycol on Chromosorb activated earth.

The pure materials are analyzed by IR spectroscopy to confirm the structures of the products:

The monounsaturated indanone has a very sweet musk. precious woody odor. When incorporated in soap and detergent over a 3-month period in quantities up to 0.1%. the odor imparted by this indanone remains strong and pleasant. and there is nodiscoloration of the soap during this time.

The epoxyindanone has a sweet. rich musk and amber odor with a fine, strong dry out. The ratio of the monounsaturated indanone to the epoxyindanone using the process of this Example is 4: 1.

Peak

Multiplet at 2.17 ppm Singlets at 1.18, 1.04,

0.98 and 0.92 ppm Doublet at 0.87 ppm.

Diffuse quartet at 1.55 ppm I-lultiplet at 1.80-2.00 ppm t-tdethylene protons (adjacent Methine proton Methylene proton INFRARED ANALYSIS OF THE 'lETRAHYDROJ-INDANONE Peak (M icrons) Interpretation with the organic phase, and solvent is stripped from the organic phase.

The resulting material has a very fine and woody musk odor. IR and PMR analysis confirm the structures 6.02 Conjugated carbonyl b l to b present:

. and

6.17 Conjugated carbon-twcarbon EXAMPLE III double bond H c 7.22 and 7.36 gem-D|meth \'l grou g Preparation of Soap Compositions W s t A-total of 100 grams of soap chips (from a toilet soap prepared from tallow and coconut oil) is mixed with one gram of the perfume composition given below until a substantially homogeneous composition is obtained. EXAMPLE ll The soap composition manifests a characteristic a. Production of S-Methoxy-I,l.13r3-pentamethylinwoody'amber dune Theperfume composition comprises the following Into a 100 ml reaction flask equipped with cooling mgreqlents: Ingredient Parts coils, stirrer, thermometer. and reflux condenser are N introduced 2.7 grams sodium hydride (52.5%) and "s Oil 40 20.0 grams dimethyl formamide. While stirring the I flask contents 12.0 grams of l.1.2.3,3-pentamethyl-5- Sandal tmqOil Loo indanol and 20.0 grams of dimethyl formamide are added one hour with sufficient cooling so that the tem- Civet Extract (3%) 5 perature does not rise above 50C and the reaction gg' mggg mixture is stirred to complete the evolution of hydrol p t gen. Dimethyl sulfate (7.6 g) is added to the reaction gglf fffiffigi I88 mixture and the temperature is maintained at 50C. 1.000

Fifty milliliters of water and 10 ml of toluene are added and the organic phase is separated from the Similar results are obtained when the mixture of Examaqueous phase. The aqueous phase is extracted with 10 PIE 1 s replaced with the ketone mixture Of Example 11 ml toluene and combined withthe organic phase which or the individual ketones of Examples 1 or II. is then washed once with 10 ml of 5% aqueous HCl and twice with 10 ml water. The solvent is stripped from the EXAMPLE washed material to obtain 12.0 grams ofcrude oil layer. Preparation of Detergent Composition This crude oil layer is distilled to obtain a liquid having total of loo grams of a detergent l f is mixed an n,,'- of 1.5185. IR and PMR analysis confirm the Wlth 9- grams of f Perfume iomposmon as set structure of the purified Compound to be 5 methoxy forth m E xample lIl until a substantially homogeneous 11233 pemamethylindune 4 composition having a woody-amber or amber-musk h. Preparation of 6. 7-Dihydro-1,l,2,3,3-pentamethyl hke odor Obtamed- 5(4l-l l-indanone and 7.7a-Dihydro-l.1,2,3,3- EXAMPLE v pentamethyl-5(6H)-indanone Into a l-liter flask equipped with thermometer. stir- Preparation, A cosmenc Powder rer. and reflux condenser are introduced 750 ml of liq- S0 A cosmenc powde? prepared by mlxmgk 100 grams uid ammonia and g of l-inch pieces of lithium ribtalcum powder wlth grams of i atone? bon (added to the ammonia with vigorous stirring) at tamed from process f l H m a ball A 3'%C. 5 ams ofthe methox 'indane and 65 ofabso- Second cometlc powder slmllarly prepared except gr l g hat the mixture re ared 1n Exam le II is re laced b lute ethanol are added during 2 hours. When addition t p p p p is complete, the reaction mass is stirred for 8 hours and the tetrahydrOmd-zwOne of Example Both-cosmenc the excess ammonia is permitted to evaporate powders have desirable woody-amber musk-like odors.

The reaction mass is poured onto 500 grams of ice to EXAMPLE VI yield an organic phase and. an aqueous phase contain- Liquid Detergent ing a precipitate. The precipitate is filtered from the Concentrated liquid detergents with a woody amber aqueous phase and the aqueous phase is then extracted musk like Odor are prepared containing 01% 0.15% with chloroform. The chloroform extract is combined and 0.20% of the mixture produced in Example with the organic layer. The total organic phase is They are prepared by ddi d homogeneously mixrrfzzzasz s25:33:31.2izzzszzlglaz a aa emica om an s i ui eter ent. The crude product is placed in a mixture of 100 ml what is clainlfed q g of 3% oxalic acid and 30 ml of ethyl acetate. and the crude mixture is refluxed for 15 minutes. The resulting material is cooled, and the aqueous phase separated from the organic phase. The aqueous phase is washed with methylene chloride, the washings are combined 1. A perfume composition containing as an essential fragrance ingredient an olfactory effective amount of 7,7a-epoxy-5,6,7,7a-tetrahydrol l ,2,3,3-pentamethyl- 4(3aH)-indanone and an auxiliary adjuvant.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION PATENT NO. 3,876,562

DATED April 8, 1975 INVENTOR(S) JOHN B. HALL it is certified that error appears in the ab0veidentified patent and that said Letters Patent are hereby corrected as shown below:

Col. 2, line 26, "5,6,6,6atetrahydro" should read 5,6,7,7atetrahydro Col. 3, lines 35 and 38, each occurrence, change "ester" to -ether Col. 5 and 6, tabulation at end of columns, heading should read "NMR SPECTRUM OF THE" Signed and Scaled this Arrest:

RUTH C. MASON C. MARSHALL DANN questing ()j'jicer (ummissimzvr 01' Parents and Trademarks 

1. A PERFUME COMPOSITION CONTAINING AS AN ESSENTIAL FRAGRANCE INGREDIENT AN OLFACTORY EFFECTIVE AMOUNT OF 7,7AEPOXY-5,6,7,7A-TETRAHYDRO-1,2,3,3-PENTAMETHYL-4(3AH)INDANONE AND AN AUXILIARY ADJUVANT. 